Process of treating hydrocarbons



Nov. 20, 1928.

Original; Filed July 19. 1918 lzvriawcr PATENT OFFICE.

GUSTAV EGIIOFF, OF CHICAGO, ILLINOIS.

Application filed July 19, 1913, Serial No.

This invention relates to improvements in process of treating hydrocarbons and refers more particularly to the treatment othigh boiling point oils such as petroleum residues,

spruce turpentine, high boiling coal tar OllS ahd the like, to convert the same into lower boiling point oils.

Among the objects of the invention are to dissociate the oil by means of an eflicient 1ntroduction into the oil in such a way as to insure the aluminum chloride thoroughly mixing with the Oll.

By the use of aluminum chloride as adissociating reagent the temperature of the oil may be kept below the normal distilling point of the highest boiling oint constituents of the oil being treated. or example, 1n some instances, it the oil boils at 750 F, 1t may be dissociated at a temperature of about 300 The variation of temperature, of course, depends very largely upon the character of oil being treated E D 4 In the presentinvention, alummum chloride may be used as such or generated 1n the body of the oil in the still by putting into e latter aluminum in the form of shavings, sheets or powder and then adding corrosive sublnnate or some other sub-catalyst-and then passing hydrogen chloride gas or chlorine gas through the body of the oil and. the solid substances in the still. Preferably, before the gases are passed through the oil the solid substances and the oil in the still are heated. The aluminum chloride forming reaction takes place more eficiently if the oil is heated he fers the gases are passed through it.

in the accompanying drawing the figure re shown illustrates an-apparatus in which invention may be carried out. the ing, 1 designates a vertical still mounted a furnace 2. A reflux condenser 3 which take the form of a conduit, in which osed'a valve l, leads from the top ill to a water cooled condenser coil 31 turn is connected to a receiving is tank 6 is provided with sight provided. with throttle valve d aluminum chloride are cirs of circulating pump 11, pipe The rate of circulation is us of valve 14. A pipe 15 id of the still 1 to the cirvalve 16 is interposed as of aluminum chloride essure gauge 8, draw-oil pipe 9,

245,592 Renewed April 21, 1928.

safety. The dotted line 18 indicates the level of the oil and the dotted line 18 the level of the aluminum chloride. e The rose 19 is at. tached to a source of chloride forming gas and controlled by valve 20. The oil is introduced by the pump which is connected toany suitable source of supply (not shown). The catalyzer is introduced through suitable manholes (not shown) and the subcatalyst in the same way. The excess chlorine and other fixed gases pass out through the gas outlet 6 cont-rolled by the valve 7. The carbon is removed b manhole plate (not shown).

In or or to more clearly practice the'invention, I give herewith an illustrative run: The method which I have found to be advantageous is to charge the still with hydrocarbon oil adding to same 1 to 2 percent aluminum powder by weight of the oil plus onetenth of one percent corrosive sublimate by weight of the oil. The oil isheated, and while heating same hydrogen chloride gas is passed through the rose (19) shown in the drawing which gas in the presence of corrosive sublimate reacts immediately with the aluminum forming aluminum chloride. Without the corrosive sublimate present the formation of the aluminum chloride is very, slow in hydrocarbon liquid. The action of the corrosive sublimate is to act catalytical- 1y with aluminum chloride in the presence of hydrocarbon liquid and also to assist in the catalysis of the said hydrocarbon liquid and I have called this corrosive sublimate a sub-catalyst and the aluminum chloride the catalyst in the reaction of forming low boiling hydrocarbons from high boiling drocarbons. The temperature of the body of oil and aluminum chloride is maintained at 450 to 500 F. and the temperature of the vapors leaving the still is maintained at 400 F. so as to produce a present marketable gasoline having an approximate end point distillation of 440 F- The pressure on the system is atmospheric, although at times a pressure of two to five pounds has developed on still, due to the fric tion of the pipes and some volatilized alumi-. num chloride passing out of the system and recondensing in the piping system. The rate I v of distillation of the hydrocarbon liquid was 10!: 3 to 5 percent of the still charge per hour. Thew percentage yield of marketable gasoline obtained using kerosene of 42 Baum gravity ranged between 23 to percent and was 'found to be dependent upon the velocity of chloride by the use of hydrogen chloride or chlorine with aluminum in the presence of hydrocarbon liquid.

The corrosive sublimate also acts as a catalyzer in forming light gravity hydrocarbon liquid from heavy gravity hydrocarbon liquid but only slightly in comparison to the aluminum chloride, hence, in this process the aluminum chloride is the normal catalyzer and corrosive sublimate the sub-catalyst.

I have found that by circulating from the still, 'oil and aluminum chloride through a spray nozzle into thestill again, that the speed of conversion of the heavy hydrocarbon oil intolight oil is much greater than by simply heating the aluminum chloride in the presence of the oil or by use of a mechanical stirrer. An enormously greater. contact surface of the aluminum chloride is attained by circulating and passing through a spray de- 'vice. -The usual method of conversion of hydrocarbon material by aluminum chloride treatment, is by means of heat, or heat and a mechanical stirrer set in the body of the oil.

From my observation of the aluminum chloride'rcaction upon hydrocarbon oil, as the reaction proceeds, the aluminum chloride layer develops a deep red color, which after a time permeates the body of the oil when starting with oils as kerosene, gas oil or lighter colored oils. The reaction area by the ordinary aluminumchloride treatment of hydrocarbon oils, is solely between liquid surfaces,

whereas my "improvement in the art gives enormously larger reaction areas in unit time,

due to circulating and spraying the liquids into the still, in a state of fine division.

I have found that my process increases the amount of product formed in a given time over the older method devised for the aluminum chloride treatment of hydrocarbon oils.

I claim as my invention:

1.'A process of treating hydrocarbon oil comprising heating said oil maintained in a substantial liquid body in the presence of aluminum chloride, maintaining a temperature within said body above the melting point of the. aluminum chloride and sufliclent to vaporize portions of the oil, withdrawing the unvaporized oil and aluminum chloride from the lower part of the liquid body and reintroducing same to the upper part of the liquid body, and continuing such circulation during the treatment, the oil and chloride being returned to the liquid body in an atomized condition.

2. A process of converting hydrocarbon oil into lower boiling point products consisting in heating the oil in a receptacle in the presence of aluminum chloride, the temperature being raised above the melting point of aluminum chloride, and sufiicient to vaporize part of the oil, removing the vapors, withdrawing the unvaporized portions and passing them, under pressure, to a zone where they are permitted to expand, in atomized form,'and retreating such unvaporized portion. 3. A process of converting hydrocarbon oil into lower boiling point products consisting in heating the oil in a receptacle in the presence of aluminum chloride, the temperature being raised above the melting point of aluminum chloride, and suflicient to vaporize part of the oil, removing the vapors, withdrawing the unvaporized portions and passing them under pressure to a zone where they are permitted to expand in atomized form.

- GUSTAV EGLOFFI 

